Process for producing a polyolefin catalyst containing ticl2, ticl3 and elemental titanium



United States Patent 3,150,107 PROCESS FQR PRODUCING A PGLYOLEFEN CATALYST CUNTAINING TiCl TiCi AND ELEMENTAL TITANIUM Donald F. Hoeg, Rockville, Frank X. Werner, Kensington, and Walter R. Wszolelr, Ellicott City, Md assiguors to W. R. Grace & Co., Clarksville, Md., a corporation of Connecticut N0 Drawing. Filed Aug. 5, 1059, Scr. No. 831,703 5 Claims. (Cl. 252-441) This invention is directed to polymerizing olefins such as ethylene and/or propylene in the substantial absence of contaminants or inhibitors such as moisture, oxygen, acetylene, acetone, hydrogen sulfide, and the like, under moderate pressures in the presence of a catalyst made by grinding titanium dichloride in an inert medium similarly free of contaminants.

The catalyst so prepared has been found to be much more active in olefin polymerization than titanium dichloride that has not been so prepared. The reason for the increased activity is not fully known. It appears, however, that the freshly fractured surfaces of the ground particles are extremely active if not allowed to come in contact with moisture, oxygen, or certain other poisons, and that such surfaces may account for the increase in activity. It further appears that this increase cannot be accounted for by an increase in surface area.

The TiCl catalyst so prepared is useful in making high-molecular weight polyolefins from monomers such as ethylene, propylene, and mixtures thereof. It is operable at temperatures ranging from room temperature up to 270 C. and higher, and at pressures from a few atmospheres, e.g., 100 p.s.i.g., to 5000 p.s.i.g., and even higher. For practical operation, however, temperatures in the range of 50-200 C. and pressures of 200 to 500 psi. are suitable.

The polymerization reaction is operable with or without a solvent. If a solvent is used, it should be one which is liquid under the conditions of temperature and pressure used, and which contains no contaminants as aforesaid. Hydrocarbon solvents are preferred, e.g., pentane, hexane, heptane, cyclohexane, octane, benzene, xylene, toluene, and the like.

The amount of catalyst is not critical. Relatively small amounts are operable to form relatively large amounts of polymer. In general, a practical range is 0.001 to 1 g. of catalyst per gram of olefin polymerized. Even larger amounts are operable, but unnecessary.

The following examples illustrate the invention, but do not limit it.

EXAMPLE 1 Grinding TiCl Catalyst Into a 1-liter stainless steel jar containing about half its bulk volume of /z-inch stainless steel balls was placed 40 g. of commercial TiCl (Sample A-l).

The ball-milling was carried out under very pure, thoroughly dried lamp-grade nitrogen for 2 /2 days. The rolls were rotated at about 200-300 rpm. The ball-mill was then opened in a dry box maintained under a slight pressure of nitrogen of the same purity, and the product was there transferred to a storage vessel. This TiCl is herein identified as Sample A Screen analyses of the product before and after milling are given in Table I below.

TABLE I Screen Analyses of TiCl Catalyst Before and After Milling The increase in the amount of material in the 1 mm.- mesh range appears to be due to the agglomeration of smaller particles by electrostatic or Van der Waals forces.

The material before milling was black and had a granular crystalline appearance. After milling it was still black, but had a soft amorphous appearance. In general, after milling, it is extremely pyrophoric.

It is essential that the TiCl be ground in the substan tial absence of oxygen, moisture, and similar contaminants, e.g., CO, acetylene, NH and ethers, ketones, and other oxygen-containing organic material. (Olefins and saturated hydrocarbons, however, are not contaminants.) We have found that lamp-grade nitrogen, e.g., nitrogen of a purity suitable for filling light bulbs, is suitable. Also suitable are the pure noble gases, especially helium, neon, and argon. The same precautions against contaminants applicable in milling also apply to handling, storing, and using the milling material.

In a similar run, TiCl was ball-milled under nitrogen for 24 hours, giving Sample B.

In a still further run, TiCl was ground. by hand with mortar and pestle for 40 minutes in a dry box under argon to provide Sample C.

The Samples A-2, B, and C, are effective catalysts for the polymerization of olefins, each being more active after milling than before.

The material can, in fact, be ground with comparable results in a high vacuum.

Any grinding (milling) at all under inert conditions will increase the activity of the TiCl to some extent. However, the preferred procedure is to grind the material thoroughly for at least several hours, e.g., 5 to 300 hours, or even longer. Ball milling overnight is suitable and even longer periods are operable. Substantially any mechanism that causes the individual pieces of T iCl to break up into smaller pieces and/ or causes their surfaces to be cleaned or abraded can be used, e.g., mortar and pestle, ball mill, rod mill, pebble mill, jet (or colloid) mill, and the like.

Throughout this specification it will be understood that all samples of activated TiCl are weighed and added to the autoclave under inert conditions equivalent to the conditions of activation as regards freedom from contaminants.

EXAMPLE 2 Synthesis of Polyethylene With Ground TiCl Using the aforesaid precautions, 0.58 g. Sample A-2 was placed in a l-liter stainless steel autoclave equipped with stirrer, thermowell, rupture disc, a ball valve serving 3 as catalyst inlet, and an inlet for charging solvent and gases. Next, 300 cc. of pure, dry cyclohexane, solvent was added. The stirrer was then turned on, and the autoclave was heated to about 140 C. Then the autoclave 4 EXAMl LE 12 As above pointed out, exposure to oxygen, etc., poisons the catalyst. This effect is further demonstrated in this n p A50 example. The catalyst poisoned in this way, however, connected 9 h 6thylene l pmcsund l may be reactivated by further grinding, as below noted. p.s.1.g., and maintained under this ethylene pressure A glass min of 250 capacity containing 495 throughout the run. The ethylene used was likewise T1012 and 230 g. of flint pebbbs under argon was placed y y and quite P f- I on a ball mill. Before milling the sample had substan- The run Proceeds (LYPmaly) at a toemperature l tially the same mesh analysis of the material of Sample between about 140 and about 160 C. Cons derable in Table I above. Tbs sample was thgn Pbb1e Var 1at1n mmpamwre however pcsslblg m using milled, and beginning with the third day specimens were acnvamd z- After 1/2 hour the run f and withdrawn at various intervals under dry argon and their the autoclave Was Cooled (to below the boiling; 170ml of respective activities tested by substantially the same prosob/ant) and Was Vented and opened 5133 Poly cedure of Example 2. The results are shown in Table ethylene-containing reaction slurry in cyclohexane was 15 HI, following; then transferred to a liter beaker. At this stage the prod- TABLE III uct was black, owing to the TiCl content. The yield of u k u crude polymer was 18 g effect of Re-lllzllmg Poisoned Catalyst If desired, the crude material may be purified and re- Sample withdrawn covered by techniques well known in the art. For excrter day, number: Activity ample, the material may be refluxed with alcoholic acids, 0 (control: tested before milling) 0.1 e.g., HC1-methanol, followed by filtration and drying. 3 2.0 The product purified as above was found to be or ex- 4 2.75 tremely high density, i.e., with an average molecular 7 (milled over week-end) 4.7 weight in excess of 100,000. 8 9.3 Using the well known formula for determining catalyst 11 15.0 activity (grams of polymer/ grams of catalyst/per hour} 15 (ambient air admitted to mill for few secit will be seen that this particular catalyst has an activity of onds ca 0.5 18 24 3.3 =5- .6 "0 2S 1 0.5s o.5 3 5 4 In a comparable run, using TiCl; that had not been when l g 'f to exclude molsturei l E ball-milled and having substantially the screen analysis and gspscl a4y aftel the dry box has 9 dner by of Sample A1, 1.18 g. of catalyst was used for 1 hour s 9 llgtelnal P IL o very pure nitrogen, argon, with a yield of 3 g. of polyethylene. The catalyst activity 9 t a like Or tWO or tree 9 5 an especlany marked improvement in catalyst activity will generally be noted, was therefore 3 e.g., as shown 1n the following table. m :25 In the following table the polymerization procedure and X apparatus were substantially the same as for Example 2. Since the yield was smaller and the amount of catalyst 40 The solvent in each run was toluene (1.66 lb.). The and the reaction time greater, it is clear that ball-milling catalyst was TiCl ball-milled under argon, for 119 hours. gives a much more active catalyst. In another control All material handling was done in a dry box under argon. run (at a lower temperature) 1.86 g. of finely divided TABLE IV TiCl of commerce, not ground under inert conditions, was used as the catalyst to polymerize ethylene in cyclo- Polyethylene hexane at 120-13-O C. under 450 p.s.i.g. for 3% hours. l N g n, s, me, The yield of polyethylene was 5 g. The catalyst activity O Dem was therefore y 5 or 0.83 1.46 150-19 470 17 50.5 0. 9490 1.22 123M2 1. 490 30 89.5 0. 9422 Further runs carried out using the activated TiClof 5 ligtggg 2381283 32 23:? 8: this invention and substantially the same techniques of 151-184 8 0 .8 0.9514 Example 2 above are summarized in Table H, below.

TABLE II Polymerization of Ethylene and Propylene Using Ground TiCl Catalyst Exam. No. Monomer Catalyst, g. Solvent Temp, G. Total press, Reaction Yield p.s.i.g. time, hours polymer, g.

Ethylene 1 0.54 None 27-33 (not 450 18 8 heated). do 1.5 do s0 450-4s0 1s 31 do 1.5 300ml. cy- 440499 2 13.5

clohexane. -do 1.02 500 m1. 390-465 2.75 40 cyclohexane do 0.68 do 410485 2 29 do 0.54 do 410-485 2 24 Propylene 1.49 300 m1. 200-360 5 20 cyclohexane 0 98 do Room temp. 130 1-2 1.27 do -114 130485 3.25 5

1 Ball-milled under nitrogen for 15 hours. 2 Ball-milled under nitrogen for 25 hours. 3 Ball-milled under nitrogen for 60 hours. 4 Bal1-ml1led under argon for 60 hours.

EXAMPLE 17 As already mentioned, the milled TiCl catalyst is also effective with ethylene-propylene mixtures. E.g., using the general procedure of Example 2, 1.32 g. of TiCl (ball-milled 5 days under argon), 300 ml. purified cyclohexane, and 22 ml. liquid propylene was placed in the autoclave, which was then sealed and heated to 145 C. When it reached this temperature it was pressured with ethylene to 450 psi. The polymerization was run at 140 C. for 32 minutes, after which the autoclave was vented, cooled, and the polymer recovered. The purified polymer had a density of about 0.93 and a propylene content of about 6% (by infra-red measurement). On pressing it gave a rubbery film.

There are certain curious changes in the TiCl mass on ball milling.

Firstly, the surface area (square meters per gram) increases, rapidly at first, then more slowly, reaching a peak at about 5 days, more or less, depending somewhat on apparatus load, milling rate, etc. Ordinarily, this area peak does not correspond with catalyst activity peak, which generally occurs well before the area peak. After the area peak is reached, further milling causes a gradual decline in area. With this area decline, activity also declines, and may drop surprisingly toward the 8th to 12th day of milling. (Such catalyst, however, is nevertheless much more active than one that has not been ground at all.)

Secondly, the TiCl slowly disproportionates to TiCl and Ti, according to the following equation:

3 TiCl 2 TiCl +Ti Referring to Table V it will be evident that the decrease in TiCl and the increase in TiCl and Ti can be accounted for by the mechanism of the foregoing equation.

(Incidentally, it may be here noted that the TiCl of commerce, being generally made from TiCl and Ti, may be expected to contain small amounts of these two materials.)

The reasons why grinding TiCl increases its activity as a polyethylene catalyst are not clearly understood. As shown in Table V, the surface area of the catalyst is increased by grinding, as may be expected. However, it is equally clear that activity is not a simple function of surface area. For example, the surface area of the catalyst of Example 21 is 27 sq. meters per gram, with an activity of 93.7, whereas the surface area of the catalyst of Example 19 is only 10.7, but with an activity of 121.2. Also, in comparing the catalysts of Examples 18 and 19, it is noted that increasing the surface area by a factor of 3-5 increases the activity by a factor of about 70. In considering the TiCl content of the ground catalysts, it will be observed that activity is roughly correlated to the percentage of TiCl in the catalyst. On the other hand, the percent of TiCl in a ground catalyst is always less than that in an unground catalyst owing to the disproportionation reaction above discussed, and yet the unground catalyst is much less active than the ground catalyst. Accordingly, activity cannot be said to be a firm function of TiCl content.

in TABLE v Physical and Chemical Changes Occurring While Ball l dilling TiCl Days Exam milled Percent Percent Percent Catalyst Surface No. (under 'liClz T101 Ti activity are argon) mfl/gm The two following examples provide more complete working data for the catalysts of Example 18 and 19.

EXAMPLE 18 Following the procedure of Example 2, 0.71 gram of unground TiCl catalyst was placed in the autoclave with 0.66 pound of toluene. The polymerization temperature was 148-166 C., the pressure was 475-540 p.s.i., the reaction time was 1 hour and 3 minutes, and the yield of solid polyethylene was 1.3 grams.

EXAi-JPLE 19 Following the procedure of the preceding example, 1.08 grams of the catalyst was used, the polymerization temperature being 154-168" C., the pressure 420-450 p.s.i., the reaction time 30 minutes, and the yield, 65.5 grams. The solvent was 0.66 pound toluene.

The uses of the polyolefins of this invention are analogous to those prepared by prior art procedures. The solid polymers can be used to make moldings, film, filament, pipe, tubing, and the like, using substantially the same equipment and technique customary for the solid polyolefins of the prior art.

This application is a continuation in part of our copending SN. 687,614, filed October 2, 1957, now abandoned.

We claim:

1. The method of activating TiCl that comprises grinding a feed consisting essentially of TiCl under inert conditions for 1-6 days to give a resultant ground TiCl containing about 39-77% TiCl 17-50% TiCl and 2-8% Ti, and having a surface area of about 11-27 square meters per gram.

2. The method according to claim 1 in which the TiCl is ground in an atmosphere of an inert vapor.

3. The method according to claim 2 in which the vapor is nitrogen.

4. The method according to claim 2 in which the atmosphere is a noble gas.

5. The method according to claim 4 in which the gas is argon.

References Cited in the file of this patent UNITED STATES PATENTS 2,893,984 Seelbach et al. iuly 7, 1959 2,956,050 Benning Oct. 11, 1960 FOREIGN PATENTS 533,362 Belgium May 16, 1955 1,132,506 France Nov. 5, 1956 1,134,740 France Dec. 3, 1956 777,538 Great Britain June 26, 1957 

1. THE METHOD OF ACTIVATING TICL2 THAT COMPRISES GRINDING A FEED CONSISTING ESSENTIALLY OF TICL2 UNDER INERT CONDITIONS FOR 1-6 DAYS TO FIVE A RESULTANT GROUND TICL2 CONTAINING ABOUT 39-77% TICL2, 17-50% TICL3, AND 2-8% TI, AND HAVING A SURFACE AREA OF BOUT 11-27 SQUARE METERS PER GRAM. 